Quaternary alkynoxymethyl amines

ABSTRACT

This invention relates to quaternaries of alkynoxymethyl amines and uses thereof. These may be summarized by the following formulae: ##STR1## where R and R&#39; are substituted groups such as alkyl, aryl, etc.; R&#39;&#39;&#39; is an acetylenic group; and X is an anion; and ##STR2## where R and R&#39;&#39;&#39; having the same meaning as in (1) and Z is a bridging group, preferably hydrocarbon such as alkylene, alkinylene, alkenylene, arylene, etc.

This is a division, of application Ser. No. 556,330, filed Mar. 7, 1975, now abandoned.

Application Ser. No. 496,145 filed Aug. 9, 1974 relates to alkynoxymethyl amines, and most preferably bis (alkynoxymethyl) amines, and to uses for these compositions particularly as corrosion inhibitors. The present invention relates to quaternaries of the alkynoxymethyl amines of Ser. No. 496,145.

The compositions of Ser. No. 496,145 are ideally illustrated by the following equation:

    RNH.sub.2 +CH.sub.2 O+R'''OH→RN(CH.sub.2 OR''').sub.2

where R is a substituted group, preferably hydrocarbon such as alkyl, aryl, aralkyl cycloalkyl, etc., and substituted derivatives thereof, etc., and R''' is an alkynyl moiety. Specific R groups illustrated herein include alkyl groups in the range of 3 to 18 carbon atoms, benzyl and cyclohexyl.

The reaction of Ser. No. 496,145 is carried out by reacting the amine, aldehyde, and acetylenic alcohol under dehydrating conditions. The alkynoxymethyl amine is formed. In practice the amine is gradually added to a mixture of formaldehyde and acetylenic alcohol in an azeotropic solvent at reflux until the theoretical amount of water is removed. Thereupon the product is separated from the reaction mixture, for example by distillation under reduced pressure.

A wide variety of amines having at least one primary group can be employed. They include aliphatic, cycloaliphatic, aryl, heterocyclic, etc. amines. These amines may or may not contain other groups. The following are representative examples.

n-Butyl amine

2-ethylhexyl amine

Monoisopropanolamine

Hexylamine

Heptylamine

Octylamine

Decylamine

Furfurylamine

Dodecylamine

Monoethanolamine

n-Amylamine

Sec-amylamine

2-amino-4-methylpentane

4-amino-2-butanol

5-isopropylamino-1-pentanol

Also, high molecular weight aliphatic amines known as Armeen 10, Armeen 16D, Armeen HTD, Armeen 18D, and Armeen CD can be used. (RNH₂). Armeens are a series of amines possessing aliphatic chains ranging from 8 to 18 carbons. Armeen 18D has the composition, 97% primary amine of which 93% is octadecyl amine according to Zimmerman and Lavine, Handbook of Material Trade Names, 1953, page 62.

Amines having ring structures include cyclohexylamine, and various comparable amines with alkyl substituents in the ring.

Similarly, an amine, presumably obtained from Rosin Amine D and acrylonitrile, can be prepared. The structure of Rosin Amine D is as follows: ##STR3##

The acetylenic alcohols employed in the present invention may suitably include ethyl octynol, propargyl alcohol, hexynol and other acetylenic alcohols having the structural formula:

    H--C.tbd.C--R"OH

where R" is ##STR4## such as ##STR5## where R₃ is selected from the group consisting of CH₃ and H and R₄ is selected from the group consisting of hydrogen, alkyl groups having 1 to 18 carbon atoms, naphthalyl, phenyl, and alkyl substituted phenyls having 1 to 10 carbon atoms in the alkyl substituent. Examples of such alcohols include: methyl butynol, methyl pentynol, hexynol, ethyl octynol, propargyl alcohol, benzyl butynol, naphthalyl butynol, and the like. Acetylenic alcohols which contain 3 to 10 carbon atoms are preferred. R" is an alkylidene radical.

Although formaldehyde is preferred, other aldehydes or ketones may be employed in place of formaldehyde such as those of the formula ##STR6## where R₁ and R₂ are hydrogen or a hydrocarbon group such as alkyl, i.e., methyl, ethyl, propyl, butyl, etc.; aryl, i.e., phenyl, alkyl phenyl, etc., benzyl; cycloalkyl, i.e., cyclohexyl, etc. Thus, the --CH₂ -group in the formula

    RN(CH.sub.2 OR''').sub.2

also may include substituted --CH₂ -- groups ##STR7## where the R₁ and R₂ are hydrogen or group derived from the aldehyde or ketone.

The following examples are illustrative of the compositions of Ser. No. 496,145.

EXAMPLE 1A

Into a 500 ml. three-necked flask provided with a reflux condenser, stirrer, and a dropping funnel were placed 30.0 g. (1 mole) of paraformaldehyde, 57.0 g. (1 mole) of propargyl alcohol, and 100 ml. of benzene. The mixture was heated to reflux and 29.5 g. (0.5 mole) of isopropyl amine was added over a thirty minute period. A Barret type water separator was placed between the flask and the reflux condenser and refluxing was continued until the theoretical amount of water was removed azeotropically. Vacuum distillation of the products gave 45.0 g. (46%) of the desired product. It had the following structure:

    C.sub.3 H.sub.7 N(CH.sub.2 O CH.sub.2 C.tbd.CH).sub.2

Analysis for C₁₁ H₁₇ NO₂ (195): %N calc. 7.18, %N found 7.39 %C calc. 67.69, %C found 67.40, %H calc. 8.71, %H found 9.07.

EXAMPLE 2A

In a similar manner, 60.0 g. (2 mole) of paraformaldehyde, 114.0 g. (2 mole) propargyl alcohol and 73.0 g. (1 mole) of butyl amine were reacted together. Vacuum distillation of the products gave 141.0 g. (68%) of the desired compound. It had the following structure:

    C.sub.4 H.sub.9 N(CH.sub.2 O CH.sub.2 C.tbd.CH).sub.2

Analysis of C₁₅ H₁₉ NO₂ (209): %N Calc. 6.68, %N found 6.81 %C Calc. 68.90, %C found 68.33, %H calc. 9.09, %H found 9.14.

EXAMPLE 3A

In a similar manner, 95.5 g. (0.5 mole) of Primene 81-R, 30.0 g. (1 mole) of paraformaldehyde, and 57.0 g. (1 mole) of propargyl alcohol were reacted together. The product had the following structure:

    t--C.sub.12 H.sub.25 --C.sub.14 H.sub.29 N(CH.sub.2 O CH.sub.2 C.tbd.CH).sub.2

Analysis: %N calc. 4.3, %N found 5.1.

EXAMPLE 4A

In a similar manner 129.0 g. (1 mole) of t-octyl amine, 60.0 g. (2 mole) of paraformaldehyde, and 114.0 g (2 mole) of propargyl alcohol were reacted together. Vacuum distillation of the products gave 113 g. (42.5%) of the desired compound. It had the following structure:

    t--C.sub.8 H.sub.17 N(CH.sub.2 O CH.sub.2 C.tbd.CH).sub.2

Analysis for C₁₆ H₂₇ NO₂ (265): %N calc. 5.28, %N found 5.30. %C calc. 72.45, %C found 72.14, %H calc. 10.19, %H found 10.39.

EXAMPLE 5A

In a similar manner 107.0 g. (1 mole) of benzyl amine, 60.0 g. (2 mole) of paraformaldehyde, 114.0 g. (2 mole) of propargyl alcohol were reacted together. Vacuum distillation of the products gave 102 g. (42%) of the desired compound. It had the following structure: ##STR8##

Analysis for C₁₅ H₁₇ NO₂ (243): %N calc. 5.76, %N found 6.06 %C calc. 74.07, %C found 73.74 %H calc. 6.99, %H found 6.98

EXAMPLE 6A

In a similar manner 99.2 g. (1 mole) of cyclohexylamine, 60.0 g. (2 mole) of paraformaldehyde, and 114.0 g. (2 mole) of propargyl alcohol were reacted together. Vacuum distillation of the products gave 90.0 g. (38.3%) of the desired compound. It had the following structure:

    Cyclohexyl-N(CH.sub.2 O CH.sub.2 C.tbd.CH).sub.2

Analysis for C₁₄ H₂₁ NO₂ (235): %N calc. 5.95, %N found 5.96 %C calc. 71.49, %C found 71.24 %H calc. 8.94, %H found 8.98

EXAMPLE 7A

In a similar manner 95.5 g. (0.5 mole) of Primene 81-R, 30,0 g. (1.0 mole) of paraformaldehyde, and 98.0 g. (1 mole) of Airco OW-1 (crude hexynol) were reacted together.

EXAMPLE 8A

In a similar manner 126.0 g. (0.4 mole) of Primene JMT, 24.0 g. (0.8 mole) of paraformaldehyde, and 45.6 g. (0.8 mole) of propargyl alcohol were reacted together.

EXAMPLE 9A

In a similar manner 105 g. (0.5 mole) of Armeen C, 30.0 g. (1 mole) of paraformaldehyde, and 57.0 g. (1 mole) of propargyl alcohol were reacted together.

EXAMPLE 10A

In a similar manner 48.0 g. (0.25 mole) of Primene 81-R, 15.0 g. (0.5 mole) of paraformaldehyde, and 21.0 g. (0.5 mole) of 2-methyl-3-butyn-2-ol were reacted together.

Examples 7A-10A yielded products corresponding to the formula RN(CH₂ OR''')₂.

In order to avoid repetitive detail the following table is presented to further illustrate examples of the compositions of Ser. No. 496,145.

                  TABLE 1A                                                         ______________________________________                                         RN(CH.sub.2 OR"C CH).sub.2                                                       R                   R"                                                       ______________________________________                                         Ex. 11 A                                                                               t-C.sub.12 H.sub.25 to t-C.sub.14 H.sub.29                                                      ##STR9##                                              Ex. 12 A                                                                               C.sub.12 H.sub.25                                                                               ##STR10##                                             Ex. 13 A                                                                               t-C.sub.12 H.sub.25 to t-C.sub.14 H.sub.29                                                      ##STR11##                                             Ex. 14 A                                                                               C.sub.6 H.sub.11                                                                                ##STR12##                                             Ex. 15 A                                                                               C.sub.6 H.sub.5 CH.sub.2                                                                        ##STR13##                                             Ex. 16 A                                                                               C.sub.4 H.sub.9                                                                                 ##STR14##                                             ______________________________________                                    

While the compounds of Ser. No. 496,145 may be isolated from the reaction mixture by vacuum distillation, in most cases it is more practical to use the reaction mixtures, as is, in preparing the quaternaries of this present invention.

The quaternaries of the present invention are prepared by reacting quaternizing agents with the alkynoxymethyl amines of Ser. No. 496,145.

The quarternary agents employed have the general formulae:

I. Monofunctional Quaternizing Agents

R'X where R' is a group which is preferably hydrocarbon such as alkyl, alkenyl, alkinyl, cycloalkyl, aryl, etc. and X is an anion, preferably a halide.

II. Difunctional Quaternizing Agents

XZX where Z is a bridging group such as alkylene, alkenylene, alkynylene, alkaralkylene, alkylene-ether-containing, an ester-containing group and X is an anion, preferably a halide.

The following are representative examples. Compounds I are prepared by reacting 1 mole of monofunctional quaternizing agent with 1 mole of alkynoxymethyl amines and Compounds II are prepared by reacting 1 mole of difunctional quaternizing agent with 2 moles of alkynoxymethyl amines according to the equations: ##STR15##

(1) Examples of Monofunctional Quaternizing Agents

Any hydrocarbon halide, e.g., alkyl, alkenyl, cycloalkenyl, aralkyl, etc., halide which contains at least one carbon atom and up to about thirty carbon atoms or more per molecule can be employed to alkylate the products of this invention. It is especially preferred to use alkyl halides having between about one to about eighteen carbon atoms per molecule. The halogen portion of the alkyl halide reactant molecule can be any halogen atom, i.e., chlorine, bromine, fluorine, and iodine. In practice, the alkyl bromides and chlorides are used, due to their greater commercial availability. Non-limiting examples of the alkyl halide reactant are methyl chloride; ethyl chloride; propyl chloride; n-butyl chloride; sec-butyl iodide; t-butyl fluoride; n-amyl bromide; isoamyl chloride; n-hexyl bromide; n-hexyl iodide; heptyl fluoride; 2-ethyl-hexyl chloride; n-octyl bromide; decyl iodide; dodecyl bromide; 7-ethyl-2-methyl-undecyl iodide; tetradecyl bromide; hexadecyl bromide; hexadecyl fluoride; heptadecyl chloride; octadecyl bromide; docosyl chloride; tetracosyl iodide; hexacosyl bromide; octacosyl chloride; and triacontyl chloride. In addition, alkenyl halides can also be employed, for example, the alkenyl halides corresponding to the above examples. In addition, the halide may contain other elements besides carbon and hydrogen, as, for example, where dichloroethylether is employed.

The alkyl halides can be chemically pure compounds or of commercial purity. Mixtures of alkyl halides, having carbon chain lengths falling within the range specified hereinbefore, can also be used. Examples of such mixtures are mono-chlorinated wax and mono-chlorinated kerosene. Complete instructions for the preparation of mono-chlorowax have been set forth in U.S. Pat. No. 2,238,790.

Thus, the term quaternizing as employed herein and in the claims include alkenylation, cycloalkenylation, aralkylation, etc., and other hydrocarbonylation as well as alkylation itself.

(2) Examples of Difunctional Quaternizing Agents

X--Z--X may be a wide variety of compounds, capable of joining amino groups, where Z may be alkylene, alkenylene, alkynylene, alkaralkylene, an alkylene-ether-containing group, an ester-containing group, etc., and X is a halide.

The following are non-limiting examples:

(I) Saturated Dihalides

    X--Z--X

where Z is alkylene, straight chain or branched, for example X(CH₂)_(n) X where n is 2-25 or more, for example 2-10, but preferably 2-4. The

    --CH.sub.2).sub.n

may be branched such as where at least one of the H's is a hydrocarbon group such as alkyl, i.e., methyl, ethyl, etc., substituted such as halo, hydroxy, etc.

(II) Aralkylene Dihalides

    X--Z--X

where Z is aralkylene having for example 8-30 or more carbons, such as 8-20 carbons, but preferably xylylene.

The following are illustrative examples: ##STR16##

Additional examples of aralkylene radicals include those of the formula --CH₂ --Ar--CH₂ -- where Ar is ##STR17##

(III) Alkylene Ethers

    X--A--X

where A is an alkylenether radical --A(OA)_(n) where A is alkylene (including cycloalkylene ether radicals) having for example from 1-10 or more carbons such as 1-4, but preferably 2 in each alkylene unit. Typical examples are ##STR18##

Additional examples of A include groups of the formula (AO)_(n) where A is ##STR19## where Y is alkyl, for example ##STR20## etc.

Thus, A can be methylene, polymethylene, ethylene, propylene, butylene, octylene, etc. In addition (AO)_(n) may be homo or hetero as to A, to yield for example (ETO)_(a) (PrO)_(b), or (PrO--ETO)_(n) ;

    --CH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.2 --

etc.

These compounds also include the formal of ethylene chlorohydrin and bromohydrin, for example ClCH₂ CH₂ OCH₂ OCH₂ CH₂ Cl,

    ClCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 Cl

etc.

(IV) Unsaturated Dihalides

    X--Z--X

where Z is an unsaturated aliphatic radical, for example

    --CH.sub.2 --CH═CH--CH.sub.2 --

    --CH.sub.2 --C.tbd.C--CH.sub.2 --

etc.

The following examples are illustrative of the present invention.

EXAMPLE 1

Into a 500 ml. three-necked flask provided with a reflux condenser and stirrer were placed 84 g. (0.4 mole) of N,N-di(propynoxymethyl)butyl amine, 57 g. (0.4 mole) of methyl iodide, and 100 ml. of ethanol. The reaction mixture was heated to reflux and held there for 24 hours.

The solvent was removed under reduced pressure on a rotary evaporator. The product was a water soluble viscous liquid. It had the following structure: ##STR21##

Anal. %I.sup.⊖ calc. 36.18 %I .sup.⊖ found 35.92

EXAMPLE 2

In a similar manner 84 g. (0.4 mole) of N,N-di (propynoxymethyl) butyl amine and 51 g. (0.4 mole) of benzyl chloride and 100 ml. of ethanol were refluxed together for 24 hours. The product was isolated as a viscous water soluble liquid. It had the following structure: ##STR22##

Anal. %Cl .sup.⊖ calc. 10.42 %Cl .sup.⊖ found 9.53

EXAMPLE 3

In a similar manner 71 g. (0.3 mole) of N,N-di (propynoxymethyl) hexyl amine, 43 g. (0.3 mole) of methyl iodide, and 100 ml. of n-propanol were refluxed for 40 hours. The product was isolated as a crystalline solid. It had the following structure: ##STR23##

Anal. %.sup.⊖ calc. 33.50 %I .sup.⊖ found 32.95

EXAMPLE 4

In a similar manner 73 g. (0.3 mole) of N,N-di (propynoxymethyl) benzyl amine, 43 g. (0.3 mole) of methyl iodide, and 100 ml. of ethanol were refluxed together for 48 hours. The isolated product was a very viscous liquid. It had the following structure: ##STR24##

Anal. %I .sup.⊖ calc. 32.99 %I .sup.⊖ found 31.64

EXAMPLE 5

In a similar manner 77 g. (0.4 mole) of N,N-di (propynoxymethyl) propyl amine, 57 g. (0.4 mole) of methyl iodide, and 100 ml. of ethanol were refluxed together for 24 hours. The product was isolated as a water soluble liquid. It had the following structure: ##STR25##

Anal. %I .sup.⊖ calc. 37.68 %I .sup.⊖ found 36.21

EXAMPLE 6

In a similar manner 79.5 g. (0.3 mole) of N,N-di (propynoxymethyl) t-octyl amine, 43 g. (0.3 mole) of methyl iodide, and 125 ml. of 2-propanol were refluxed together for 72 hours. The product was isolated as a resinous solid that was soluble in water. It had the following structure: ##STR26##

Anal. %I .sup.⊖ calc. 31.20 %I .sup.⊖ found 31.35

EXAMPLE 7

In a similar manner 77 g. (0.4 mole) of N,N-di (propynoxymethyl) isopropyl amine, 57 g. (0.4 mole) of 1-bromopropane, and 125 ml. of 2-propanol were refluxed together for 36 hours. The product was isolated as a yellow liquid. It had the following structure: ##STR27##

Anal. %Br .sup.⊖ calc. 23.64 %Br .sup.⊖ found 22.90

EXAMPLE 8

In a similar manner 164 g. (0.5 mole) of N,N-di (propynoxymethyl) t-dodecyl amine, 71 g. (0.5 mole) of methyl iodide and 200 ml. of 2-propanol were refluxed together for 60 hours. The isolated product had the following structure: ##STR28##

EXAMPLE 9

In a similar manner 164 g. (0.5 mole) of N,N-di (propynoxymethyl) t-dodecyl amine, 64 g. (0.5 mole) of benzyl chloride and 200 ml. of 2-propanol were refluxed together for 60 hours. The isolated product had the following structure: ##STR29##

Anal. %Cl ⁻ calc. 7.8 %Cl ⁻ found 7.1

EXAMPLE 10

In a similar manner 160 g. (0.5 mole) of N,N-di (propynoxymethyl) n-dodecyl amine, 71 g. (0.5 mole) of methyl iodide, and 200 ml. of 2-propanol were refluxed together for 60 hours. The isolated product was a viscous water soluble liquid that foamed in water. It had the following structure: ##STR30##

Anal. %I .sup.⊖ calc. 27.4 %I .sup.⊖ found 25.4

EXAMPLE 11

In a similar manner 164 g. (0.5 mole) of N,N-di (propynoxymethyl) n-dodecyl amine, 64 g. (0.5 mole) of benzyl chloride, and 200 ml. of n-propanol were refluxed together for 48 hours. The isolated product was a viscous liquid that foamed in water. It had the following structure: ##STR31##

Anal. %Cl .sup.⊖ calc. 7.8 %Cl .sup.⊖ found 7.0

EXAMPLE 12

In a similar manner 94 g. (0.4 mole) of N,N-di (propynoxymethyl) cyclohexylamine, 57 g. (0.4 mole) of methyl iodide, and 120 ml. of n-propanol were heated at reflux for 48 hours. The isolated liquid product had the following structure: ##STR32##

Anal. %I .sup.⊖ calc. 33.70 %I .sup.⊖ found 32.98

In order to avoid repetitive detail the following table was constructed to further illustrate examples of this invention.

    ______________________________________                                          ##STR33##                                                                       R           R'        R"            X.sup.⊖                          ______________________________________                                         Ex. 13 C.sub.12 H.sub.25                                                                        C.sub.2 H.sub.5                                                                          ##STR34##    Br                                     Ex. 14 C.sub.4 H.sub.9                                                                          CH.sub.3                                                                                 ##STR35##    I                                      Ex. 15 C.sub.3 H.sub.7                                                                          CH.sub.3                                                                                 ##STR36##    I                                      Ex. 16 C.sub.6 H.sub.5 CH.sub.2                                                                 C.sub.2 H.sub.5                                                                          ##STR37##    Br                                     Ex. 17 t-C.sub.4 H.sub.9                                                                        CH.sub.3                                                                                 ##STR38##    I                                      Ex. 18 C.sub.4 H.sub.9                                                                          CH.sub.3 CH.sub.2      SO.sub.4                               Ex. 19 C.sub.14 H.sub.29                                                                        CH.sub.3 CH.sub.2      I                                      Ex. 20 i-C.sub.3 H.sub.7                                                                        C.sub.12 H.sub.25                                                                       CH.sub.2      Br                                     ______________________________________                                    

EXAMPLE 21

Into a 500 ml. three-necked flask equipped with a stirrer and reflux condenser were introduced 164 g. (0.5 mole) of N,N-di(propynoxymethyl) n-dodecyl amine, 54 g. (0.25 mole) of 1,4-dibromobutane and 150 ml. of n-propanol. This mixture was heated at reflux for 72 hours. The isolated product was a sticky solid that foamed greatly in water. It had the following structure: ##STR39##

EXAMPLE 22

In a similar manner 104 g. (0.5 mole) of N,N-di (propynoxymethyl) butyl amine, 54 g. (0.25 mole) of 1,4-dibromobutane and 150 ml. of 2-propanol were refluxed together for 48 hrs. The isolated product was a viscous water soluble liquid. It had the following structure: ##STR40##

Anal. %Br .sup.⊖ calc. 37.64 %Br .sup.⊖ found 36.92

EXAMPLE 23

In a similar manner 77 g. (0.4 mole) of N,N-di (propynoxymethyl) propyl amine, 25 g. (0.2 mole) of 1,4-dichlorobutene-2, and 100 ml. of n-propanol were refluxed together for 48 hours. The isolated product had the following structure: ##STR41##

In order to avoid repetitive detail the following table was constructed to further illustrate examples of this invention.

    ______________________________________                                          ##STR42##                                                                      R         R"           Z             X.sup.⊖                          ______________________________________                                         Ex.  C.sub.4 H.sub.9                                                                          CH.sub.2   (CH.sub.2).sub.6                                                                             Br                                     24                                                                             Ex. 25                                                                              C.sub.12 H.sub.25                                                                        CH.sub.2                                                                                   ##STR43##    Cl                                     Ex.  i-C.sub.3 H.sub.7                                                                        CH.sub.2   CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                                         Cl                                     26                                                                             Ex. 27                                                                               ##STR44##                                                                                ##STR45## CH.sub.2 CH.sub.2                                                                            Br                                     Ex.  C.sub.14 H.sub.25                                                                        CH.sub.2   (CH.sub.2).sub.4                                                                             Br                                     28                                                                             Ex.  C.sub.12 H.sub.25                                                                        CH.sub.2   CH.sub.2 CHCHCH.sub.2                                                                        Cl                                     29                                                                             ______________________________________                                    

USES

This invention also relates to the inhibition of corrosion, particularly the corrosion of metals in contact with the acid solutions.

The present invention is especially useful in the acidizing or treating of earth formations and wells traversed by a bore hole. It may also be used in metal cleaning and pickling baths which generally comprise aqueous solutions of inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid and are useful in the cleaning and treatment of iron, zinc, ferrous alloys, and the like.

If no corrosion inhibitor is present when the aqueous acidic solution comes in contact with the metal, excessive metal loss and consumption or loss of acid, and other adverse results will be experienced. There has been a continuing search for corrosion inhibitors which can be used effectively in small concentrations, and which are economical to produce. The need is also for corrosion inhibitors which are effective at high temperatures, e.g., 200° F. and above, such as are found in operations involving acidic solutions, particularly oil-well acidizing where higher and higher temperatures are found as the well extends further into the earth.

While the compounds of this invention are of themselves particularly good acid corrosion inhibitors, optionally they may be blended with acetylenic alcohols, dispersing and solubilizing agents such as ethoxylated phenols, alcohols, and fatty acids. They may also be blended with such known acid inhibitors as the quinoline or alkyl pyridine quaternary compounds or synergists such as terpene alcohols, formamide, formic acid, alkyl amine, alkylene polyamines, heterocyclic amines, and the like.

Quaternary ammonium compounds may be illustrated by C-alkyl pyridine-N-methyl chloride quaternary, C-alkyl pyridine-N-benzyl chloride quaternary, quinoline-N-benzyl chloride quaternary, isoquinoline-N-benzyl chloride quaternary, thioalkyl pyridine quaternaries, thioquinoline quaternaries, benzoquinoline quaternaries, thiobenzoquinoline quaternaries, imidazole quaternaries, pyrimidine quaternaries, carbazole quaternaries, the corresponding ammonium compounds, pyridines and quinolines may also be used alone or in combination with the quaternary compounds. Thus a pyridine plus quinoline quaternary, a quinoline plus quinoline quaternary, or quinoline or amine alone or in combination may be used.

The formic acid compound may be selected from the esters and amides of formic acid. The formic acid compound may be from the group consisting of formate esters of the structure:

    HCOOR

where R is a monoaryl group, an alkyl group having 1 to 6 carbon atoms, cyclo-alkyl residues having 5 to 6 carbon atoms, alkenyl and alkynl groups having 2 to 6 carbon atoms which may contain functional groupings selected from --C--OH, --OH, ═C═O, --COOH, --SH, and NH₂. Examples of the formic acid compound are: methyl formate, ethylformate, benzyl formate, other alkyl and aryl formates, and the like. Other examples include formamide, dimethyl formamide, formanilide, and the like. Mixtures of the esters and mixtures of the amides may be used.

USE AS PICKLING INHIBITORS

This phase of the invention relates to pickling. More particularly, the invention is directed to a pickling composition and to a method of pickling ferrous metal. The term "ferrous metal" as used herein refers to iron, iron alloys and steel.

To prepare ferrous metal sheet, strip, etc. for subsequent processing, it is frequently desirable to remove oxide coating, formed during manufacturing, from the surface. The presence of oxide coating, referred to as "scale" is objectionable when the material is to undergo subsequent processing. Thus, for example, oxide scale must be removed and a clean surface provided if satisfactory results are to be obtained from hot rolled sheet and strip in any operation involving deformation of the product. Similarly, steel prepared for drawing must possess a clean surface and removal of the oxide scale therefrom is essential since the scale tends to shorten drawing-die life as well as destroy the surface smoothness of the finished product. Oxide removal from sheet or strip is also necessary prior to coating operations to permit proper alloying or adherence of the coating to the ferrous metal strip or sheet. Prior to cold reduction, it is necessary that the oxide formed during hot rolling be completely removed to preclude surface irregularities and enable uniform reduction of the work.

The chemical process used to remove oxide from metal surfaces is referred to as "pickling." Typical pickling processes involve the use of aqueous acid solutions, usually inorganic acids, into which the metal article is immersed. The acid solution reacts with the oxides to form water and a salt of the acid. A common problem in this process is "overpickling" which is a condition resulting when the ferrous metal remains in the pickling solution after the oxide scale is removed from the surface and the pickling solution reacts with the ferrous base metal. An additional difficulty in pickling results from the liberated hydrogen being absorbed by the base metal and causing hydrogen embrittlement. To overcome the aforementioned problems in pickling, it has been customary to add corrosion inhibitors to the pickling solution.

The present invention avoids the above-described problems in pickling ferrous metal articles and provides a pickling composition which minimizes corrosion, overpickling and hydrogen embrittlement. Thus the pickling inhibitors described herein not only prevent excessive dissolution of the ferrous base metal but effectively limit the amount of hydrogen absorption thereby during pickling. According to the invention, a pickling composition for ferrous metal is provided which comprises a pickling acid such as sulfuric or hydrochloric acid and a small but effective amount of the compounds of this invention, for example at least about 5 p.p.m., such as from about 100 to 50,000 p.p.m., from about 500-30,000 p.p.m., but preferably from about 3,000 to 10,000 p.p.m.

Ferrous metal articles are pickled by contacting the surface (usually by immersion in the pickling solution) with a pickling composition as described to remove oxide from their surface with minimum dissolution and hydrogen embrittlement thereof and then washing the ferrous metal to remove the pickling composition therefrom.

USE IN ACIDIZING EARTH FORMATIONS

The compositions of the invention can also be used as corrosion inhibitors in acidizing media employed in the treatment of deep wells to reverse the production of petroleum or gas therefrom and more particularly to an improved method of acidizing a calcareous or magnesium oil-bearing formation.

It is well known that production of petroleum or gas from a limestone, dolomite, or other calcareous-magnesian formation can be stimulated by introducing an acid into the producing well and forcing it into the oil or gas bearing formation. The treating acid, commonly a mineral acid such as HCl, is capable of forming water soluble salts upon contact with the formation and is effective to increase the permeability thereof and augment the flow of petroleum to the producing well.

Corrosion Test Procedure

In these tests the acid solutions were mixed by diluting concentrated hydrochloric acid with water to the desired concentrations.

Corrosion coupons of N-80 steel (ASTM) were pickled in an uninhibited 10% HCl solution for 10 minutes, neutralized in a 10% solution of NaHCO₃, dipped in acetone to remove water and allowed to dry. They were then weighed to the nearest milligram and stored in a desicator.

In most of the tests, a 25 cc/in² acid volume to coupon surface area ratio was used. After the desired amount of acid was poured into glass bottles, the inhibitor was added. The inhibited acid solution was the placed in a water bath which had been set at a predetermined temperature and allowed to preheat for 20 minutes. After which time, the coupons were placed in the preheated inhibited acid solutions. The coupons were left in the acid solutions for the specified test time, then removed, neutralized, recleaned, rinsed, dipped in acetone, allowed to dry, then reweighed.

The loss in weight in grams was multiplied times a calculated factor to convert the loss in weight to lbs./ft² /24 hrs. The factor was calculated as follows: ##EQU1##

The results of these tests are included below:

    ______________________________________                                                                                   Corros-                                                                        ion                                                                            Rate                                        Conc.   Test    Test               (lbs./                                      in      Temp.   Time         Metal ft.sup.2 /                           Inhibitor                                                                             p.p.m.  °F.                                                                             Hrs.  Acid   Type  day                                  ______________________________________                                         Ex. 1  6000    200     4     15% HCl                                                                               N-80  0.385                                Ex. 2  6000    200     4     15% HCl                                                                               N-80  0.474                                Ex. 4  6000    200     4     15% HCl                                                                               N-80  0.550                                Ex. 5  6000    200     4     15% HCl                                                                               N-80  0.323                                Ex. 6  6000    200     4     15% HCl                                                                               N-80  0.384                                Ex. 7  6000    200     4     15% HCl                                                                               N-80  0.043                                Ex. 8  6000    200     4     15% HCl                                                                               N-80  0.033                                Ex. 9  6000    200     4     15% HCl                                                                               N-80  0.045                                Ex. 10 6000    200     4     15% HCl                                                                               N-80  0.024                                Ex. 17 6000    200     4     15% HCl                                                                               N-80  0.033                                Ex. 18 6000    200     4     15% HCl                                                                               N-80  0.435                                Ex. 21 6000    200     4     15% HCl                                                                               N-80  0.025                                Blank  6000    200     4     15% HCl                                                                               N-80  2.240                                ______________________________________                                    

Applications in which the inhibitors of the present invention are particularly useful include oil-well acidizing solutions, metal pickling, cleaning and polishing baths, boiler cleaning compositions and the like. They are also useful as oil soluble corrosion inhibitors, bactericides, water-in-oil demulsifying agents, surfactants and the like.

USE IN BRINES

This phase of the invention relates to the prevention of corrosion in systems containing a corrosive aqueous medium, and most particularly in systems containing brines.

More particularly, this invention relates to the prevention of corrosion in the secondary recovery of petroleum by water flooding and in the disposal of waste water and brine from oil and gas wells. Still more particularly, this invention relates to a process of preventing corrosion in water flooding and in the disposal of waste water and brine from oil and gas wells which is characterized by injecting into an underground formation an aqueous solution containing minor amounts of compositions of this invention, in sufficient amounts to prevent the corrosion of metals employed in such operation. This invention also relates to corrosion inhibited brine solutions of these compounds.

When an oil well ceases to flow by the natural presure in the formation and/or substantial quantities of oil can no longer be obtained by the usual pumping methods, various processes are sometimes used for the treatment of the oil-bearing formation in order to increase the flow of the oil. These processes are usually described as secondary recovery processes. One such process which is used quite frequently is the water flooding process wherein water is pumped under pressure into what is called an "injection well" and oil, along with quantities of water, that have been displaced from the formation, are pumped out of an adjacent well usually referred to as a "producing well." The oil which is pumped from the producing well is then separated from the water that has been pumped from the producing well and the water is pumped to a storage reservoir from which it can again be pumped into the injection well. Supplementary water from other sources may also be used in conjunction with the produced water. When the storage reservoir is open to the atmosphere and the oil is subject to aeration this type of water flooding system is referred to herein as an "open water flooding system." If the water is recirculated in a closed system without substantial aeration, the secondary recovery method is referred to herein as a "closed water flooding system."

Because of the corrosive nature of oil field brines, to economically produce oil by water flooding, it is necessary to prevent or reduce corrosion since corrosion increases the cost thereof by making it necessary to repair and replace such equipment at frequent intervals.

I have now discovered a method of preventing corrosion in systems containing a corrosive aqueous media, and most particularly in systems containing brines, which is characterized by employing the compositions of this invention.

I have also discovered an improved process of protecting from corrosion metallic equipment employed in secondary oil recovery by water flooding such as injection wells, transmission lines, filters, meters, storage tanks, and other metallic implements employed therein and particularly those containing iron, steel, and ferrous alloys, such process being characterized by employing in water flood operation the compositions of this invention.

This phase of the invention then is particularly concerned with preventing corrosion in a water flooding process characterized by the flooding medium containing an aqueous or an oil field brine solution of these compounds.

In many oil fields large volumes of water are produced and must be disposed of where water flooding operations are not in use or where water flooding operations cannot handle the amount of produced water. Most States have laws restricting pollution of streams and land with produced waters, and oil producers must then find some method of disposing of the waste produced salt water. In many instances, therefore, the salt water is disposed of by injecting the water into permeable low pressure strata below the fresh water level. The formation into which the water is injected is not the oil producing formation and this type of disposal is defined as salt water disposal or waste water disposal. The problems of corrosion of equipment are analagous to those encountered in the secondary recovery operation by water flooding.

The compositions of this invention can also be used in such water disposal wells thus providing a simple and economical method of solving the corrosion problems encountered in disposing of unwanted water.

Water flood and waste disposal operations are too well known to require further elaboration. In essence, in the present process, the flooding operation is effected in the conventional manner except that the flooding medium contains a minor amount of the compound of this invention, sufficient to prevent corrosion, in concentrations of about 10 p.p.m. to 10,000 p.p.m., or more, for example, about 50 to 5,000 p.p.m., but preferably about 15 to 1,500 p.p.m. The upper limiting amount of the compounds is determined by economic considerations. Since the success of a water flooding operation manifestly depends upon its total cost being less than the value of the additional oil recovered from the oil reservoir, it is quite important to use as little as possible of these compounds consistent with optimum corrosion inhibition. Optimum performance is generally obtained employing about 1,000 p.p.m. Since these compounds are themselves inexpensive and are used in low concentrations, they enhance the success of a flood operation by lowering the cost thereof.

In addition, these compounds are not sensitive to oxygen content of the water and these are effective corrosion inhibitors in both open water flooding systems and closed water flooding systems.

While the flooding medium employed in accordance with the present invention contains water or oil field brine and the compounds, the medium may also contain other materials. For example, the flooding medium may also contain other agents such as surface active agents or detergents which aid in wetting throughout the system and also promote the desorption of residual oil from the formation, sequestering agents which prevent the deposition of calcium and/or magnesium compounds in the interstices of the formation, bactericides which prevent the formation from becoming plugged through bacterial growth, tracers, etc. Similarly, they may be employed in conjunction with any of the operating techniques commonly employed in water flooding and water disposal processes, for example five spot flooding, peripheral flooding, etc., and in conjunction with other secondary recovery methods.

USE IN ACID SYSTEMS

The compounds of this invention can also be employed as corrosion inhibitors for acid systems, for example as illustrated by the pickling of ferrous metals, the treatment of calcareous earth formations, etc., as described in the following sections.

Static Weight Loss Tests

The test procedure involves the measurement of the corrosive action of the fluids inhibited by the composition herein described upon sandblasted S.A.E. 1020 steel coupons measuring 7/8 by 31/4 inches under conditions approximating those found in an actual producing well, and the comparison thereof with results obtained by subjecting identical test coupons to the corrosive action of identical fluids containing no inhibitor.

Clear pint bottles were charged with 200 ml. of 10% sodium chloride solution saturated with hydrogen sulfide and 200 ml. of mineral spirits and a predetermined amount of inhibitor was then added. In all cases the inhibitor concentration was based on the total volume of the fluid. Weighed coupons were then added, the bottles tightly sealed and allowed to remain at room temperature for 72 hours. The coupons were then removed, cleaned by immersion in inhibited 10% HCl, dried and weighed.

The changes in the weight of the coupons during the corrosion test were taken as a measurement of the effectiveness of the inhibitor compositions. Protection percentage was calculated for each test coupon taken from the inhibited fluids in accordance with the following formula:

    (L.sub.1 -L.sub.2)/L.sub.1 ×100=% Protection

in which L₁ is the loss in weight of the coupons taken from the uninhibited fluids and L₂ is the loss in weight of coupons which were subjected to the inhibited fluids.

    ______________________________________                                         Static Weight Loss Test                                                                   Concentration                                                       Ex.        p.p.m.      % Protection                                            ______________________________________                                          8         100         97.5                                                     9         100         98.6                                                    10         100         96.4                                                    12         100         95.8                                                    17         100         98.7                                                    21         100         97.4                                                    23         100         92.3                                                    ______________________________________                                    

Another test was conducted in order to determine the effectiveness of the corrosion inhibitors of the present invention in the corrosive medium, tap water.

Coupons of mild steel (S.A.E. 1018) having dimensions of 5 cm×3.5 cm×0.32 cm were sandblasted and cleaned. They were then weighed and placed in open beakers containing tap water to which predetermined amounts of inhibitor had been added. The beakers containing the fluid were allowed to remain at room temperature for 96 hours. The coupons were then removed, cleaned, immersed in acetone, dried, and weighed.

The changes in the weight of the coupons during the corrosion test were taken as a measurement of the effectiveness of the inhibitor compositions. Protection percentage was calculated as the ratio of the difference between the coupon weight loss with the blank and the coupon weight loss using the inhibitor, divided by the coupon weight loss of the blank, multiplied by 100.

    ______________________________________                                         Static Weight Loss Test                                                                   Concentration                                                       Ex.        p.p.m.      % Protection                                            ______________________________________                                          8         100         98.4                                                     9         100         97.6                                                    10         100         95.3                                                    12         100         96.5                                                    17         100         97.4                                                    21         100         98.2                                                    23         100         95.1                                                    ______________________________________                                    

The compositions of this invention are useful as microbiocides such as in water treatment, water flooding in secondary recovery of oil, treating hydrocarbons, etc.

For the above type of systems one generally employs from about 10 to 1,000 p.p.m., such as from about 20-750 p.p.m., for example from about 30-500 p.p.m., but preferably about 50-150 p.p.m. Variation above or below this amount will depend on the particular composition actually employed. Microbial Testing: The screening procedure was as follows: a one percent by weight solution of the test compound in water was prepared. The solution was aseptically added to a sterile broth that would support the growth of the test organism, "Desulforibrio desulfuricans," to provide a concentration of 20, 30, 40, 50 and 100 parts by weight of test compound per million parts by weight of broth. A general growth medium, such as prescribed by the American Petroleum Institute was used. The broth containing the test compound then was dispersed in 5 cc amounts into sterile disposable tubes and the tubes were inoculated with the growing test organism and incubated at 35° C. for 24 hours. The absence or presence of growth of the microorganisms was determined by visual inspection by an experienced observer.

Following is a summary of the results of the testing of examples of this invention.

    ______________________________________                                                         Concentration of                                               Compound Example No.                                                                           Test Compound (p.p.m.)                                         ______________________________________                                          8              50                                                              9              30                                                             10              50                                                             12              30                                                             17              40                                                             21              50                                                             23              50                                                             ______________________________________                                    

For microbiocidal use, one employs about 5-500 p.p.m., such as from about 10-300 p.p.m., for example from about 20-200 p.p.m., but preferably from about 30-100 p.p.m. Variations above or below this amount will depend on the particular composition actually employed.

In all of the above tests no growth of the test organism occurred, thus indicating that the compound is biostatic or a biocide.

NOTE: The compounds used were diluted to 50% by weight in isopropyl alcohol prior to testing.

Reduction of Surface Tension

The compounds of this invention possess surfactant properties in aqueous solutions.

Tensiometer: Du Nouy Tensiometer, 6 mm platinum ring.

    ______________________________________                                                        Concentration percent                                                          by weight in distilled                                                         water                                                                          0.1    0.01                                                                    Dynes/sq. cm.                                                   ______________________________________                                         Ex. 9            35       38                                                   Ex. 10           37       40                                                   Ex. 12           42       47                                                   Ex. 18           35       39                                                   Ex. 19           36       39                                                   Ex. 20           34       38                                                   Ex. 24           36       40                                                   Ex. 25           37       41                                                   Surface tension of                                                             distilled water  72                                                            ______________________________________                                     

I claim:
 1. A process of inhibiting corrosion which comprises treating a system with a quaternary alkynoxymethyl amine halide having one to two quaternary nitrogen atoms to each of which are attached up to two alkynoxymethyl moieties, the groups directly attached to the quaternary nitrogen atoms in the said quaternary amines being said alkynoxymethyl groups and being R and R' groups when there is but one quaternary nitrogen atom present per molecule and being said alkynoxymethyl groups and being R and Z groups when there are two quaternary nitrogen atoms present per molecule, the Z groups constituting bridging groups linking the two quaternary nitrogen atoms, the R groups being monovalent hydrocarbon, hydroxy substituted alkyl, or furfuryl groups, the R' groups being monovalent hydrocarbon, and Z groups being divalent alkylene, alkenylene, alkynylene, alkaralkylene, or alkyleneether groups, and said alkynoxymethyl groups having the formula HC.tbd.CR"OCH₂ --, where R" is alkylidene.
 2. The process of inhibiting corrosion which comprises treating a system with a quaternary according to claim 1 of the formula ##STR46## where R and R' are hydrocarbon groups, R" is alkylidene, and X.sup.⊖ is a halide anion.
 3. The process of inhibiting corrosion which comprises treating a system with a quaternary according to claim 1 having the formula ##STR47## where R and R' are hydrocarbon group, R" is alkylidene, X.sup.⊖ is a halide anion and Z is a bridging group.
 4. The process of treating a system which comprises employing as a microbiocide a quaternary alkynoxymethyl amine halide having one to two quaternary nitrogen atoms to each of which are attached up to two alkynoxymethyl moieties, the groups directly attached to the quaternary nitrogen atoms in the said quaternary amines being said alkynoxymethyl groups and being R and R' groups when there is but one quaternary nitrogen atom present per molecule and being said alkynoxymethyl groups and being R and Z groups when there are two quaternary nitrogen atoms present per molecule, the Z groups constituting bridging groups linking the two quaternary nitrogen atoms, the R groups being monovalent hydrocarbon, hydroxy substituted alkyl, or furfuryl groups, the R' groups being monovalent hydrocarbon, the Z groups being divalent alkylene, alkenylene, alkynylene, alkaralkylene, or alkyleneether groups, and said alkynoxymethyl groups having the formula HC.tbd.CR"OCH₂ --, where R" is alkylidene.
 5. The process of treating a system which comprises employing as a surfactant a quaternary alkynoxymethyl amine halide having one to two quaternary nitrogen atoms to each of which are attached up to two alkynoxymethyl moieties, the groups directly attached to the quaternary nitrogen atoms in the said quaternary amines being said alkynoxymethyl groups and being R and R' groups when there is but one quaternary nitrogen atom present per molecule and being said alkynoxymethyl groups and being R and Z groups when there are two quaternary nitrogen atoms present per molecule, the Z groups constituting bridging groups linking the two quaternary nitrogen atoms, the R groups being monovalent hydrocarbon, hydroxy substituted alkyl, or furfuryl groups, the R' groups being monovalent hydrocarbon, the Z groups being divalent alkylene, alkenylene, alkynylene, alkaralkylene, or alkyleneether groups, and said alkynoxymethyl groups having the formula HC.tbd.CR"OCH₂ --, where R" is alkylidene.
 6. The process according to claim 4 where the quaternary has the formula ##STR48## where R and R' are hydrocarbon groups, R" is alkylidene, and X.sup.⊖ is a halide anion.
 7. The process according to claim 4 where the quaternary has the formula ##STR49## where R and R' are hydrocarbon groups; R" is alkylidene, X.sup.⊖ is a halide anion and Z is a bridging group.
 8. The process according to claim 2 where R and R' are alkyl, aryl or aralkyl.
 9. The process according to claim 3 where R and R' are alkyl, aryl or aralkyl.
 10. The process according to claim 6 where R and R' are alkyl, aryl or aralkyl.
 11. The process according to claim 7 where R and R' are alkyl, aryl or aralkyl.
 12. The process according to claim 8 where the quaternary has the formula ##STR50##
 13. The process according to claim 9 where the quaternary has the formula ##STR51##
 14. The process according to claim 10 where the quaternary has the formula ##STR52##
 15. The process according to claim 11 where the quaternary has the formula ##STR53##
 16. The process according to claim 5 where the quaternary has the formula ##STR54## 